CA1091690A

CA1091690A - Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids

Info

Publication number: CA1091690A
Application number: CA245,314A
Authority: CA
Inventors: Martin C. Cornell, Iii; Dennis L. Schmidt; George A. Doorakian
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1976-01-19
Filing date: 1976-02-09
Publication date: 1980-12-16
Also published as: JPS52108499A; DE2609474A1; DE2609474B2; DE2609474C3; US4131633A

Abstract

ABSTRACT

This invention concerns a process comprising reaction of a vicinal epoxide with a phenolic com-pound, a carboxylic acid, or a carboxylic acid an-hydride in presence of a catalyst corresponding to the formula wherein each R is a C1-20 hydrocarbyl radical, and R' is , where R1 is H or a C1-20 hydrocarbyl radical, R2 is H
or C1-20 alkyl, R3 represents hydrogen, C1-20 alkyl, carboxy, or C1-20 alkoxycarbonyl; n is ? to 20 and A.THETA.
is an anion. The invention also concerns a composition comprising an epoxy resin containing an average of more than one vicinal epoxy group per molecule and a catalyst as defined above. These catalysts are effective for selectively promoting the desired reactions to give high yields of products having excellent color. However, the catalysts are substantially unreactive with epoxy resins at ambient temperatures and are thus useful for the pre-paration of precatalyzed epoxy resin compositions.

Description

~l~9i6'r~() This invention pertalns to epoxy re~in com-positions and process of reacting vicinal epoxides with phenols, carboxylic acids, or anhydrides of such acids. Such reactions are commercially important in that functional monomers (e.g. hydroxyethyl acrylate), hydraulic fluids (e~g. 2-phenoxyethanol) and high molecular weight linear or cross-linked epoxy resins are thus produced.
The reactions between epoxides and phenols, carboxylic acids or anhydrides have been extensively studied and these classes of reactants are well known in the prior art.
It is well known in the prior art that (1) a catalyst is required to attain a satisfactory reac-tion rate and ~2) those skilled in the art recognize that the reaction between epoxides and phenols is not, mechanistically speaking, the same as the re-action between epoxides and carboxylic acids (or anhydrides) due to the diferences in products.
Substantially linear polymers are produced by reac-ting epoxy resins with polyfunctional phenols in the presence of a catalyst, whereas cross-linkPd polymers are produced by reacting the same epoxy resins with a polycarboxylic acid (or anhydride) in the presence of the same catalysts. The reactive species which catalyze the reaction is therefore believed to be different in each instance. Thus, compounds which catalyze one reaction would not necessarily be ex-pected to catalyze the other.

'~

16,973A-F -1-~t~3~

Several problems have been encountered in using many of the prior art catalysts. In many in-stances, the catalysts react with the epoxy reactant and thus preclude the option of marketing a blend comprising an epoxy resin and a catalyst; this blend is commonly referred to as a "precatalyzed epoxy resin". In other instances, the problem associated with the prior art catalysts is selectivity; i.e.
the catalysts simultaneously promote the reaction between the epoxy reactant and the phenolic hydroxyl group (or acid group) on the reactant and the ali-phatic hydroxyl group(s) on the product giving branched or cross-linked polymers rather than the desired lin-ear p~lymers. In still other instances, the reaction rate is unsatisfactory and/or the product is highly colored and therefore unsatisfactory for many uses.
Sometimes, the product is contaminated with corrosive anions (e.g. chloride) and is therefore unacceptable for electrical encapsulation (potting).
It has now been found that certain phos-phorus containing compounds are latent catalysts for promoting the reaction between vicinal epoxides and phenols and/or carbox~lic acids (or anhydrides).
The catalysts are surprisingly effective in selec-tively catalyzing the desired reaction between the reactants at a suitable reaction rate. The reaction products are obtained in high yields and are generally of excellent color. Additionally, the catalysts are surprisingly unreactive with epoxy resins at conven-tional storage temperatures. As a result, precatalyzed 16,973A-F -2-1~9i~;~0 epoxy resins can now be produced by merely blending the subject catalysts with the epoxy resins. Such precatalyzed epoxy resins are, of course, novel compositions of matter.
Accordingly, the present invention provides an epoxy resin composition which comprises (a) an epoxy resin containing an average of more than one vicinal ep~xy group per molecule and (b) a catalyst for reaction of the epoxy resin with a phenolic compound, a carboxylic acid, or a carboxy~i'c acid anhydride, which catalyst corresponds to the for~mula (R)3P ~ - R' ~
wherein each R represents a Cl 6 alkyl radical or a phenyl radical and R' represents -CH(CHR )nCOOH, or -CH(CHRl)nCOOR A ~ , COo ~ ` 3 where Rl represents a hydrogen atom; R2 represents a hydrogen atom or a Cl 6 alkyl radical; R3 represents a hydrogen atom, a methyl or a carboxy radical; n represents 0, 1 or 2; and A ~ represents an anion. Preferred catalysts are those wherein each R represents Cl 6 alkyl or phenyl, and~Rl and R2 represent hydrogen, and n is 0, 1 or 2. The most effective catalysts appear to be those wherein each R is n-butyl.
Suitable anions include, for example, chloride, bromide, iodide, acetate, diacetate, chloroacetate, ~16~

trifluoroacetatet cyanide thiocyanate, tetraphenyl-borate, toluenesulfonate, 2-ethylhexanoate, cyano~
acetate, sulfonyldiacetate, acetone dicarboxylate, bisulfate, trifluoromethylsulfonate, t-butoxide, and nitrate. Preferred anions are the halides, acetate, and chloroacetate on ~he basis of availability and the efficacy of compounds containing them.
This invention further provides the process of reacting (a) a vicinal epoxide-containing compound with (b) a phenolic compound, a carboxylic acid, a carboxylic acid anhydride, or a mixture thereof in presence of a catalyst as defined hereinbefore.
The above phosphorus-containing compounds are particularly useful in catalyzing the reaction between vicinal epoxides and phenols, carboxylic acids, or anhydrides. In this utility, the amount used can be varied over a wide range. Generally, however, they are used in a small but catalytic amount, as for example in amounts of from 0.001 to 10 percent by weight, based on the combined weight of reactants. Preferably, the catalyst is included in amounts of from 0.05 to 5 percent by weight.
As stated above, the reactants used are well known classes of compounds. The vicinal epoxides, for example, are organic compounds bearing one or more vicinal epoxy groups. The alkylene oxides of from

2 to 24 carbon atoms t the epihalohydrins, and thé epoxy resins are perhaps the best known and most widely used members of the genus. Ethylene oxide, propylene oxide, lj,973A-F _4_ 1~9~

1,2-butylene oxide, and epichlorohydrin are the pre-ferred monoepoxides. There are two preferred sub-classes of epoxy resins. The first subclass corres-ponds to the general formula O O O

f-CH2CHCH2 0-CH2CHCH2 I CH2CH~H2 ~ _ CH2 ~ n CH

wherein R is hydrogen or an alkyl radical and n is from 0.1 to lO, preferably from l to 2. Preparation of these polyepoxides is illustrated in USP 2,216,099 and USP 2,658 9 885. The second subclass corresponds to the general formula CH2-CH-CH2-O- ~ -A- ~ / \

R2 Rl wherein R, Rl, R2, and R3 are independently selected from hydrogen, bromine, and chlorine, and wherein A
is an alkylene (e.g. methylene) or alkylidene (e~g, isopropylidene) group having from 1 to 4 carbon atoms, -S-, -S-S-, -SO-, -SO2 , -CO-, or -O-.
The phenolic compounds are organic compounds having one or more hydroxyl groups attached to an aro-matic nucleus. This class of compounds therefore includes phenol, alpha and beta-naphthol, o-, m-, or ~-chlorophenol, alkylated derivatives of phenol 16,973A-F -5-1~91~;~0 (e.g. o-methyl-, 3,5-dimethyl-, ~-t-butyl- and ~--nonylphenol)~ and other monohydric phenols, as well as polyhydric phenols, such as resorcinol or hydro-quinone. The polyhydric phenols bearing from 2 to 6 hydroxyl groups and having from 6 to 30 carbon atoms are particularly useful in the reaction with epoxy resins to form high molecular weight resins (linear or cross-linked) useful in coatings. Pre-ferred polyhydric phenols are those corresponding to the formula R R R R

HO--~ X ~--OH

R R R R
wherein R is hydrogen, halogen (fluoro, chloro or bromo), or hydrocarbyl; and X is oxygen, sulfur, -SO-, -SO2-, bivalent hydrocarbon radicals containing up to 10 carbon atoms, and hydrocarbon radicals contain-ing oxygen, sulfur and nitrogen, such as -OR' O-, --OR'OR'O--, --S--R'--S--, --S--R' S--R'--S--, --OSiO--, --OSiOSiO--, O O O O O O
.. .. .. .. .. ..
-O-C-R' -C-O-, -C-0R' -O-C- ~ -S-R' -S- or -SO2-R'-SO2-radicals wherein R' is a bivalent hydrocarbon radical.
4,4'-Isopropylidenediphenol (bisphenol A) is the mo~t preferred phenol.
The organic carboxylic acid~ and anhydrides are likewise well known. The acids bear one or more carboxyl groups on the organic nucleus. The anhy-drides are prepared from such carboxylic acids by 16,973A-F -6-;90 the removal of water therefrom in an intra- or inter-molecular condensation. This class of compounds includes acetic, propionic, octanoic, stearic, acry-lic, methacrylic, oleic, benzoic, phthalic, iso-phthalic~ maleic, succinic, adipic, itaconic, poly-acrylic and polymethacrylic acids, and the like, and anhydrides thereof, such as acetic anhydride, phthalic anhydride, or hexahydrophthalic anhydride.
There are two subclasses of carboxylic acids and anhydrides that are particularly important based on their reaction with epoxy resins.
The reaction of ethylenically unsaturated monocarboxylic acids with epoxy resins produces hy-droxy-substituted esters or polyesters which are par-ticularly useful in the preparation of coatings and adhesives. Acrylic and methacrylic acids are parti-cularly useful in this regard. Accordingly, the ethylenically unsaturated monocarboxylic acids are a preferred subclass of acids.
The second preferred subclass of acids is comprised of members which are useful in crosslink-ing epoxy resins. The members of this subclass are normally di- or tribasic acids, or anhydrides thereof, and are prefereably liquid or low-melting solids, such as succinic, maleic, or hexahydrophthalic acids or anhydrides. Other such acids and anhydrides are known.
The ratio of vicinal epoxide reactant to phenol, carboxylic acid, or anhydride reactant in 16,973A-F _7_ ~3~ )0 the subject process can vary over a w~de ranye de-pending upon the product desired. For example, if a product terminated with a phenolic ether group is desired, obviously one would employ an excess of phenol in the process.
In many instances, the reactants are liquid and no solven~ or diluent is needed. In other cases, however, where one or both of the reactants are solid or viscous liquids, an inert solvent or diluent can be used advantageously. Suitable inert solvents or diluents are known to those skilled in the art and include ketones (such as acetone or methy ethyl ke-tone), and hydrocarbons (such as benzene, toluene, xylene, cyclohexane, or ligroin).
Generally, the reaction mix~ure is warmed at temperature in the range of from 50C to 225~C
(preferably 100-175C) until an exotherm begins7 After the exotherm has peaked, warming in the same range for an additional time to assure substantially complete reaction is conducted. Atmospheric or super-atmospheric pressures (e.g. up to about 200 psig, 14 kg./cm.2 gauge) are common.
The products produced are generally known compounds in industry. The particular product pro-duced will vary in properties depending upon the selection and ratio of reactants used in the pro-cess. The following illustrates the types of prod-ucts which can be produced.
The products produced by reacting an epoxy resin with a phenol in the presence of the 16,973A-F -8-subjeck catalysts are phenolic eth~r~ bearing one or more aliphatic secondary hydroxyl groups. Such aliphatic hydroxyl groups are formed in the ring--opening reaction between the epoxy and phenolic hydroxyl groups. ~dditionally, the reaction prod-ucts bear a terminal epoxy group(s) or a phenolic hydroxyl group(s) depending upon the ratio of re-actants. Consequently, they are reactive inter-mediates which can be cured (cross-linked) with many polyfunctional curing agents, as known in the art, to ~orm hard, insoluble solids which are useful coatings. The cured products (particu-larly thos of high molecular weight) are useful, for example, as surface coatings, as adhesive layers in laminates, coatings on filament windings, and in structural binding applications. The re-action products prepared from halogenated (parti-cularly brominated) phenols are particularly use-ful in flameproofing applications, since they-tend to be self extinguishing. Thus, they are useful in forming cured coatings for wood paneling and as adhesive layers in wood laminates.
The products produced by reacting an epoxy resin with a monocarboxylic acid (or anhydride of ~5 such acid) have terminal ester groups and are use-ful, for example, in coatings, adhesives, reinforced plastics, and moldings. The products formed by re-acting epoxy resins with polycarboxylic acids, or anhydrides thereof, are cross-linked~ insoluble resins used, for example, in coatings.

16/973A F _g_ 3i~

~unctional monomers can be produced by re-acting a C2 to C~ alkylene oxide with acrylic or meth-acrylic acid. Hydraulic flUids can be ~repared by reacting lower alkylene oxide with a phenol in sub-stantially equimolar amounts. Nonionic surfactants can be prepared by reacting an alkylated monohydric phenol with a C2 to C4 alkylene oxide or mixture of such alkylene oxides.
The catalysts employed in the invention wherein R' is -CH(CHR )nCOOH
COO~
can be prepared by reacting a phosphine of the for-mula ~R)3P with an ~-chloro acid of the formula Cl-CH(CHRl)nCOOH.
COOH
Those wherein n is 1 and R is an aliphatic hydro-carbyl radical can be prepared by hydroly~ing a compound of the formula (R~3P = C - CHR
O~C\o~c~o which may or may not be isolated from reaction of a tertiary phosphine with a maleic anhydride.
The catalysts employed in the invention wherein R' is -CH(CHRl)nCOOH A0 COOH
can be prepared by reacting the compound of the ~ormula ..~
16,973A-F -10-~3~

(R)3P~ - CH(cH~l) COO~
with a compound of the ormula H~A0.
The catalysts employed in the invention wherein R' is -CH2(CHRl) COOH A~ can be prepared by decarboxylation of those of the formula (R)3P~ - CH(CHRl)nCOOH A~
COOH
by heating. Catalysts can be prepared also by re-acting a phosphine of the formula (R)3P with an equi-molar amount of an acid of the formula X-CH(CHRl)nCOOH

where X and A~ is Cl or Br.
In most cases, the anion can be varied by conventional ion-exchange techniques.
The following illustrates preparation of the catalysts.
Tri-n-Butyl(1,2-dicarboxyethyljphosphonium Hydroxide, Inner Salt Maleic anhydride (223 g.; 2.28 moles) dis-solved in 200 ml. of acetone was added dropwise over 1.5 hours to a vigorously stirred solution of tri-n--butylphosphine (484 g.; 2.28 moles) in 1 liter of acetone at ambient conditions. The burgundy-colored reaction mixture was stirred overnight with water (86.4 g.; 4.80 moles) giving 592 g. of a pinkish--white crystalline solid which melts at 107-10~.5C
with effervescence. This product was dissolved 16,~73A-F -11-in 3000 ml. of methylene chloride, 3000 ml. of acetone was then added, and after cooling to 0C
for 4 hours, filtering, and washing with acetone, 551 g. (76% yield) of fine white needles, m. 107--108.5C with effervescence, was obtained.
Calc. for C16~31O4P: C 60.30; H 9.88; P 9.75 Found: C 60.40; H 9.93; P 10.00 Triphenyl(1,2-dicarboxyeth~l)phosphonium chloride

3-(Triphenylphosphoranylidene)dihydro-2,5--furandione (4.0 g.) was added to a mixture of 100 ml~ ace~one, 100 ml. water, and 5 ml. concentrated HCl. After 16 hours at room temperature, the re-action mixture was filtered to remove a small amount of a white solid. The filtrate was evaporated under vacuum at room temperature to give 4.1 g. (98.0~
yield) of product, m.p. 125-130C with evolution of CO2.
C _ Cl P_ . C22H20C14 63.6 4.8 8.6 7.5 Found 63.1 5.1 8.3 7.1 Triphenyl(2-carboxyethyl~phosphonium chloride 2.0 g. of triphenyl(l,2-dicarboxyethyl)-phosphonium chloride was heated at 145C for several minute~ until the evolution of carbon dioxide ceased.
The solid residue was crystallized from ethanol-ethyl acetate to give 1.66 g. (92.7% yield) of product, m.p. 196-198C
C
. C21H20ClO2P 68.0 5.4 Found 68.1 5.5 16,-73A-F -12-~3~

Tri-n-butyl(carboxyme-khyl)phosphonium chloride A rnixture o 404.6 g. tributylphosphine and 185.2 g. chloroacetic acid in 320 ml. metha-nol was stirred at room temperature for 2 hours.
Evaporation of the methanol gave a colorless, vis-cous liquid product.
Analysis: Calculated: C56.65, H10.19, P10.44 Found: C56.42, H10.21, P10.34 The following examples illustrate the in-vention.
Example 1 A mixture of 75.79 parts by weight of the diglycidyl ether of bisphenol A having an epoxy equiva-lent weight of 187, 24.21 parts by weight of bisphenol A, and 0.12 weight percent (based on total liquid) of triphenyl(l,2-dicarboxyethyl)phosphonium chloride dis-solved in methanol was heated with stirring under ni-trogen from ambient temperature to 150C at a rate of about 3 per minute. On discontinuation of the heating, the mixture exothermed to a temperature of about 215C.
After the exotherm subsided, the mixture was heated at 150C for 2.5 hours. Theoretical epoxide content =
8.20%; observed = 8O16%.
Example 2 Example 1 was repeated except using triphenyl-(2-carboxyethyl)phosphonium chloride as catalyst. The exotherm peak was about 221C. Observed epoxide con-tent - 8.0~%.
Example 3 Example 1 was repeated except using 63.9 par~s by weight of the diglycidyl ether of bisphenol 16,973A-F -13-~3~

A and 36.1 parts by weight o~ bisphenol A. The exotherm peak was about 236C. Theoretical epo-xide content = 1.00%; observed 1.45~.
Example 4 Mixtures of the diglycidyl ether of bis-phenol A and 0.041 weight percent tri-n-butyl(1,2--dicarboxyethyl)phosphonium hydroxide, inner salt were stored at 50C for various periods. After storage, the epoxide content was determined and the mixtures were reacted with bisphenol A at 160C
for 5 hours. The results were as follows.
Storage Initial Exotherm Time ~ Peak ~ Epoxide of Reaction Pxoduct Weeks Epoxide C Theoretical Ob~erved 0 22.40 232 2.10 1.94 1 22.35 232 2.06 1.77 2 22.35 233 2.06 1.78

4 21.93 228 1.80 1.78 8 21.75 217 1.67 1.82 The above shows that the catalyst retained its activity for several weeks in admixture with the epoxy resin.
Examples 5 and 6 In a manner similar to Example 1, 321.8 g.
of a diglycidyl ether of bisphenol A was reacted with 178.2 g. bisphenol A in presence of triphenyl(3-car-boxypropyl)phosphonium bromide or triphenyl(l,2-dicar-boxyethyl)phosphonium bromide. The temperature of the mixtures was raised at a rate of about 5/minute to 150C and allowed to exotherm. After the exotherm subsided, the mixtures were heated 5 hours at 180C.
The results were as follows.

16,973A-F -14-~ 6~0 Ex- Peak ample _ Catalyst _ Exotherm % Epoxide No. Kind g. C lTheoryal.oo%) 03P CH2CEI2CH2COOH Br0 0.561 237 1.81 6 03P~CHCH2COOH Br~ 0.600 233 1.945 COOH

Example 7 Tri-n-butyl(1,2-dicarboxyethyl)phosphonium hydroxide, inner salt was added at 0.15 weight percent concentration to an aliquot of a mixture consisting of a liquid epoxy resin (100 parts by weight) having an EEW of 172-176 and hexahydrophthalic anhydride (80 parts by waight). The catalyzPd mixture was formed by preheating the epoxy resin and anhydride components in separate containers to 70C and then blending such components and the catalyst with efficient stirring.
The catalyzed mixture was degassed under vacuum. Gel time at 110C was 1.5-2.0 hours. The remainder of the catalyzed mixture was poured into a ~old and heated 2 hours at 110C and 2 hours at 150C thus producing a colorless, cross-linked sheet casting having the fol-lowing pxoperties.
Tensile yield strength 12500 p.s.i. (1022 kg./cm.2) Tensile modulus 514000 p.s.i. (35980 kg./cm.
Elongation, % 4.7 Flexural strength 22000 p.s.i. (1540 kg./cm.2) Other species of the present catalysts can be si~ilarly used. In addition, the above anhydride can be replaced with other anhydrides of organic car-boxylic or polycarboxylic acids as defined above. For 16 973A~F -15-3~i'7(J

example, maleic anhy~ride could be used in the above reaction le~ding to cro~-llnked products. ~lterna-~ively, acrylic or me~hacrylic acid could be used in the above reaction leading to epoxy resins terminated with free-radical or thermally polymerizable vinyl groups. Such compounds are likewise useful coating materials.
Examples 8 and 9 Phenol and ethylene oxide (1.05 to 1.1 mole/mole of phenol) were charged to a reaction vessel under sufficient pressure to maintain the reactants in substantially liquid phase at 150C.
To this was added 0.1 weight percent of a catalyst and the reaction mixture heated with stirring for 3-4 hours at 150C. The reaction mixture was cooled and the volatiles removed under vacuum. The liquid residue was analyzed and the results are shown in Table 1.

16,~73A-F -16-t3i ~ )O

.....
h ~ ~ C5 a) u~ u~ u~
o o _ $1 ~1 ~ ~ ;` ~
~ :: .
_ C~ o~
~ o H O :I~
a~ .,~ ~
~ '~1 ~ ~1 ~

~i U~
) I ~ 0 ` O 01 h It~
~ ~1 8 m ~ ~ ~o ~
Y
c~ ~
~ ~9 ~1 ~ c~ o~

x 3.L~ O

Examples 10 and 11 Mixtures oE 386.g g. diylycidyl ether of Bisphenol A having an epoxy equivalent weight of 187, 213.6 g. bisphenol A, and a catalyst were heated at about 180C during which samples were removed peri-odically and analyzed for % epoxide (theory, 1.00~).
The catalysts employed and results were as follows.
Heating Catalyst Time, % Epoxide ~ Kind HoursObserved (n-C4Hg)3P~-CH2COOCH3 Cl~ 0 495 1.0 3.63 2.5 1.74

5.0 1.20 (n-G4Hg)3P~-CH2COOC2H5 Cl~ 0.498 1.0 4.99 2.5 1.98 5.0 1.19 The products of these examples had average molecular weights of >3500.
Example 12 and 13 Mixtures of diglycidyl ether of bisphenol A having an epoxy equivalent weight of 187, bisphenol A, and catalyst were heated 1.5 hours at 150C. The-oretical % epoxide of the products was 8.00. The catalysts employed and results were as follows.
Catalyst% Epoxide K~ wt%* Observed - -' n_c4H9)3P0-cH2cH2cooH CF3C0.15 7.96 (n~C4Hg)3P -CH2CH2COOH CH2Cl-COO~ 0.20 7.41 *based on combined weight of the reactants 16,~73A-F -18-;g~

179.79 g. o~ diglycidyl ether o bisphenol A having an epoxy equivalent weiyht of 186-192, 82.23 g.
of bisphenol A, and 62.98 g. of tall oil fatty acid were placed into a 1000 ml. flask equipped with stir-rer, condenser, water trap, thermocouple, and nitro-gen sparge, and 16.25 g. of xylene was added to aid in elimination of water of esterifcation. An amount of catalyst was added to provide 0.004 parts by weight phosphorus per 100 parks by weight of the reactants.
The mixture was heated to 230C within 30 minutes and then allowed to exotherm. When the exotherm subsi-ded, heating was continued for 2 hours at 230C. At this time a sample was taken for determination of vis-cosity.
About 105 g. more of the tall oil fatty acid was added to bring the epoxy/fatty acid ratio to 60/40, taking into account the acid previously added and the sample removed. The mixture was then heated at 250C for four hours during which samples were taken for viscosity and acid number determi-nations. The final resin was cooled and reduced to 60 percent non-volatiles with xylene. The catalysts employed and results were as follows.

16 ~73A-F -19-::
O ~1 o o c~ ~
r o~ ~ ~ , ~1 I ~ no o ~ ~+ ~ + ~E~
p~ ~

er ~ a) a~ _l ~ ,~ x ~rl rl a) ~ o o o ~ ~
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~ o c~ ~ ~ ~ ~
t~ - U --~ O ~ ~
I ~ D O O
~1 ~i3 0 ~ ~:~ t --I+ ~ ~ ~ +
11l _ . o o Z:
U
~ ,1 ,1 ~ a ~ , u ~ o~ o ~ o~ o ~ ~
U ~l Z ~rl æ ~rl z ~,, z rl rl O U~
o o ~ o ~ o ~a o ~ ~r o o o E~ L~ U-r~ h C) C.) ~`

" ~ ~ ~ U ~ U~
~J U~ X ~ h a1 a~ a ~
O ~ J ~:: S
E3 ~ .Y O ~ ~ S I h E~ E~

X ~d . O rl a) ~d ~ ~ ~ R
W C.) ~ P.~

16, 973A-F -20

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An epoxy resin composition which comprises (a) an epoxy resin containing an average of more than one vicinal epoxy group per molecule and (b) a catalyst for reaction of the epoxy resin with a phenolic compound, a carboxylic acid or carboxylic acid anhydride which catalyst corresponds to the formula wherein each R represents a C1-6 alkyl radical or a phenyl radical and R' represents or where R1 represents a hydrogen atom; R2 represents a hydrogen atom or a C1-6 alkyl radical; R3 represents a hydrogen atom, a methyl or a carboxy radical; n represents 0, 1 or 2; and A ? represents an anion.

21

3. A composition as claimed in Claim 1, or 2 wherein the anion is chloride, bromide, iodide, acetate, diacetate, chloroacetate, trifluoroace-tate, cyanide, thiocyanate, tetraphenylborate ben-zoate, toluenesulfonate, 2-ethylhexanoate, cyano-acetate, sulfonyldiacetate, acetone dicarboxylate, bisulfate, trifluoromethylsulfonate, t-butoxide, or nitrate.

4. A composition as claimed in Claim 1 wherein the catalyst is tri-n-butyl(1,2-dicarboxy-ethyl)phosphonium chloride or hydroxide inner salt.

5. A composition as claimed in Claim 1 or 6 wherein the catalyst is triphenyl(l,2-dicarboxy-methyl)phosphonium chloride or bromide.

6. A composition as claimed in Claim 1 wherein the catalyst is tri-n-butyl(carboxymethyl)-phosphonium chloride.

7. A composition as claimed in Claim 1, 2, or 8 wherein the epoxy resin is a reaction prod-uct of 4,4'-isopropylidenediphenol and epichlorohy-drin.

8. A composition as claimed in Claim 1 which contains, in addition, a phenolic compound, a carboxylic acid, or carboxylic acid anhydride.

9. A composition as claimed in Claim 1 which contains, in addition, 4,4'-isopropylidene-diphenol.

10. A composition as claimed in Claim 1 which contains, in addition, acrylic acid, meth-acrylic acid, succinic acid or anhydride, maleic acid or anhydride, or hexahydrophthalic acid or an-hydride.

11. A composition as claimed in Claim 8 wherein the catalyst is present in amount of from 0.001 to 10 percent by weight based on the combined weight of other named components.

12. A composition as claimed in Claim 8 wherein the catalyst is present in an amount of from 0.05 to 5 percent by weight based on the combined weight of other named components.

13. The process of reacting (a) a vicinal epoxide-containing compound with (b) a phenolic com-pound, a carboxylic acid, a carboxylic acid anhydride, or a mixture thereof in presence of a catalyst which corresponds to the formula (R)3P? - R'?
wherein each R represents a C1-6 alkyl radical or a phenyl radical and R' represents , or , where R1 represents a hydrogen atom; R2 represents a hydrogen atom or a C1-6 alkyl radical; R3 represents a hydrogen atom a methyl or a carboxy radical; n represents 0, 1 or 2; and A ? represents an anion.

14. The process claimed in claim 13 wherein each R is n-butyl.

15. The process claimed in claim 13 wherein the anion is chloride, bromide, iodide, acetate, diacetate, chloroacetate, trifluoroacetate, cyanide, thiocyanate, tetraphenylborate, benzoate, toluenesulfonate, 2-ethylhexanoate, cyanoacetate, sulfonyldiacetate, acetone dicarboxylate, bisulfate, trifluoromethyl sulfonate, t-butoxide, or nitrate.

16. The process claimed in Claim 13 wherein the catalyst employed is tri-n-butyl(1,2-dicarboxy-ethyl)phosphonium chloride or hydroxide inner salt.

17. The process claimed in Claim 13 wherein the catalyst employed is triphenyl(1,2-dicarboxyethyl)-phosphonium chloride or bromide.

18. The process claimed in Claim 13 wherein the catalyst employed is tri-n-butyl(carboxymethyl)-phosphonium chloride.

19. The process claimed in Claim 13 wherein the vicinal epoxide-containing compound is an epoxy resin containing an average of more than one epoxy group per molecule.

20. The process claimed in Claim 19 wherein the epoxy resin is a reaction product of 4,4'-isopro-pylidenediphenol and epichlorohydrin.

21. The process claimed in Claim 13 wherein reactant (b) is 4,4'-isopropylidenedi-phenol.

22. The process claimed in Claim 13 wherein reactant (b) is acrylic acid, methacry-lic acid, succinic acid or anhydride, maleic acid or anhydride, or hexahydrophthalic acid or anhydride.

23. The process claimed in Claim 13 wherein the catalyst is employed in an amount of from 0.001 to 10 percent by weight based on the combined weight of the reactants.

24. The process claimed in Claim 13 wherein the catalyst is employed in an amount of from 0.05 to 5 percent by weight based on the combined weight of the reactants.

25. The process claimed in Claim 13 wherein the reaction is carried out at a temperature within the range of from 50 to 225°C.

26. The process claimed in Claim 13 wherein the reaction is carried out at a temperature within the range of from 100 to 175°C.